Solvent Extractor

ABSTRACT

Supercritical extraction of diatomaceous earth results in a much more significant improvement in hydrocarbon recovery over Fischer retorting than achievable with tar sands. Process and apparatus for supercritical extraction of diatomaceous earth are disclosed.

This is a division of application Ser. No. 475,991, filed Mar. 16, 1983,now U.S. Pat. No. 4,448,669, issued May 15, 1984.

The present invention relates to the recovery of hydrocarbon values suchas oil from minerals. In a more specific aspect this invention relatesto the extraction of diatomite or diatomaceous earth. A yet morespecific aspect of this invention is an apparatus for recovery ofhydrocarbons from diatomaceous earth.

BACKGROUND OF THE INVENTION

With the increasing difficulty of finding and producing oil from oilbearing rock formations other sources of hydrocarbons have been subjectto intense investigation in recent years. Tar sands, oil shale, coal andlignite are just some examples of such other hydrocarbon sources. Manyprocesses have been described in the art for recovery of hydrocarbonfrom such minerals and/or for the conversion of such minerals intorecoverable hydrocarbons. It is known that diatomaceous earth can be anattractive candidate for hydrocarbon recovery. The prior art describessolvent extraction of oil from diatomite ore. Such a process isdescribed in U.S. Pat. No. 4,239,617. This prior art process utilizes asolvent extraction wherein a micella of oil in hydrocarbon solvent ismixed with the diatomite and the slurry is heated to near the boilingpoint of the solvent.

THE INVENTION

It is one object of this invention to provide a process for recoveryinghydrocarbons from diatomaceous earth.

A further object of this invention is to provide a highly effectivesolvent extraction process allowing a high recovery percentage ofhydrocarbons while permitting simple separation steps to separate thesolvent and the recovered hydrocarbons from the remaining solids ofdiatomite ore.

A yet further object of this invntion is to provide an apparatus foreffective recovery of hydrocarbons from diatomaceous erath.

These and other objects, advantages, details and features of thisinvention will become apparent to those skilled in the art from thefollowing detailed description of the invention, the appended claims andthe drawings in which

FIGS. 1 and 2 are a schematic view of the solvent extraction stage ofthe process and apparatus of this invention,

FIGS. 3 and 4 are a schematic view of the separation stage of theprocess and apparatus of this invention.

In accordance with this invention a process for recovering hydrocarbonvalues from diatomaceous earth is provided. This process involves thestep of subjecting a mixture of diatomaceous earth containingrecoverable hydrocarbons and a solvent to supercritical conditions withrespect to the solvent. The second step of the process of this inventionis to separate the fluid phase comprising at least a portion of thesolvent used and at least some of said recoverable hydrocarbon valuesfrom a solid phase comprising at least some of the remainingdiatomaceous earth particles.

It has surprisingly been found that supercritical extraction appears tobe uniquely suited for the extraction of diatomaceous earth. Whilesupercritical extraction of tar sand also improve hydrocarbon yield ascompared to Fischer assay recovery, the improvement using supercriticalextraction of diatomaceous earth compared with Fischer retorting wasalmost 16% higher than the comparable improvement achieved with tar sandunder essentially identical conditions. This so establishedsubstantially different behavior of diatomaceous earth as compared totar sand was unexpected and unpredictable. The process of this inventionthus makes possible a very substantial increase in hydrocarbon recoveryfrom diatomaceous earth. It appears that diatomaceous earth is uniquelysusceptible to supercritical extraction.

DIATOMACEOUS EARTH

Unladen diatomaceous earth of diatomite is a light friable siliciousmaterial derived chiefly from diatom remains. Diatoms are minuteplanktonic unicellar or colonial algea with silicified skeletons thatform diatomite. It is also called Kieselguhr or Infusorial Earth. It isa soft, white, earthy deposit of hydrated silica, being the siliceousskeletons of minute aquatic plants known as diatoms, found at Digby Neckin Canada, in Germany, the United States, and many other parts of theworld. It is generally associated with earthy impurities, and containsfrom 65 to 87 percent SiO₂, 2.3 to 11.7 percent, Al₂ O₃, up to 3 percentFe₂ O₃, small proportions of the oxides of calcium, magnesium,potassium, and sodium, and from 5 to 14 percent water.

It is of great absorbent capacity, one variety being capable of takingup about four times its own weight of water and having a sp. gr. ofabout 0.33. Calcination is often resorted to for the removal of organicmatter and improvement of color.

Diatomaceous earth, after at least a substantial portion of thehydrocarbonaceous material has been removed therefrom by the process ofthis invention, has the properties of 75-80% internal porosity, 25-50%external void fraction, 17-30 lb/cu ft bulk dry density and a surfacearea of 1.2 to 50 square meters/gram. The preferred oil ladendiatomaceous earth has the property that the oil is on the surface ofthe diatomaceous earth, i.e. that the diatomite is oil wet.

The above listed properties of diatomaceous earth are determined inaccordance with the following procedures:

Crystalline or skeletal density is calculated from composition ofdiatomaceous earth. In the above it is about 123 lb/cu ft. A mercuryporosimetry procedure can also be used to determine crystalline orskeletal density. Relationships are as given:

    ε=1-(ρ.sub.b /ρ.sub.p)                     (Eq. 1)

    x=1-(ρ.sub.p /ρ.sub.c)                             (Eq. 2)

ρ_(p) =particle density determined by liquid nitrogen displacement

x =internal porosity: calculated by Eq. 2 from particle density andskeletal or crystalline density by composition analysis

ε=external void fraction: calculated by Eq. 1 from bulk density andparticle density by liquid N₂ displacement

ρ_(b) =bulk dry density: ASTM 1982, part 25, Desig. D4164-62, 1180-1181surface area: ASTM 1978, part 25, Desig. D3663-78, pp. 808-812

ρ_(c) =crystalline or skeletal density calculated from composition ordetermined by mercury porosimetry

EXTRACTION PROCESS

The process of this invention involves supercritical extraction ofdiatomaceous earth with a solvent under supercritical conditions withrespect to the solvent and separating the fluid phase of thesupercritical extraction from a solid phase.

The temperature of the extraction step is more typically up to 150° C.,preferably about 20° C. to 50° C., above the critical temperature of thesolvent. The pressure of the supercritical extraction will be generallyup to 500 psi above the critical pressure; preferably the pressure willbe above the tangential extrapolation of the boiling point/pressurecurve for the solvent at the given temperature.

While several solvents can be used in accordance with this invention, itis presently preferred to use a substantially hydrocarbonaceous solventhaving preferably 3 to 12 carbon atoms. Particularly suitable aresolvents which are substantially aliphatic and have a number of 3 to 10carbon atoms per molecule. Aromatic solvents having 5 to 12 carbon atomsand being substantially hydrocarbons can also be utilized. Examples ofsuch solvents are pentanes, hexanes, heptanes, octanes, benzene,toluene, xylenes, tetralin and naphthalenes. Mixtures of solvents canalso be used in accordance with this invention.

Among the solvents listed above, heptane and toluene are presentlyparticularly preferred.

The separation of the solvent and hydrocarbons on the one hand and thesolid residue on the other hand can be done in a variety of ways. Thesupercritical mixture under supercritical conditions can be adjusted toa fluid/solid separation, e.g. by filtering, centrifuging or settling.Thereafter the fluid being substantially free of solid particles can besubjected to further processing and solvent recovery while the solidphase can be subjected to one or more steps for solvent recovery, suchas heating the solid mass to a temperature substantially above theboiling of the solvent utilized.

In another variation of this invention the extraction mixture containingthe solvent, the extracted hydrocarbons and the remaining solids upersupercritical conditions can be subjected to a fluid/fluid separationstep first, by either raising the temperature of the mixture or reducingthe pressure of the mixture. This step causes an at least partialseparation of the fluid material in the mixture into at least twodifferent fluid phases. With this procedure the heavier hydrocarbonmaterial, which may be resins and asphalt, can be removed together withthe solids of the diatomaceous earth while the lighter hydrocarbon oilsare recovered in the major portion of the solvent.

The mixture of solvent and extracted hydrocarbons is subjected to one ormore further separation steps in which a solvent stream beingsubstantially free of extracted hydrocarbons and a hydrocarbon materialbeing substantially free of solvent are recovered. The solvent isrecycled to the supercritical extraction step while the recoveredhydrocarbons may be subjected to further processing. Also, it ispreferred to subject the separated and hydrocarbon depleted diatomaceousearth to one or more solvent recovery steps. The so recovered solvent isalso recycled to the supercritical extraction step.

EXTRACTION APPARATUS

Another embodiment of this invention resides in an apparatus forsupercritically extracting diatomaceous earth. This apparatus comprisesan inlet chamber wherein diatomaceous earth and solvent can be broughtto supercritical conditions with respect to the solvent. In fluidcommunciation with this inlet chamber a loop reactor is provided inwhich the mixture of solvent and diatomaceous earth is circulated undersupercritical conditions. The loop reactor is provided with at least twosettling legs having means for periodic removal of materials settled inthese legs. This allows the separation and removal of solvent richmixtures of hydrocarbon depleted diatomaceous earth particles and afluid comprising both solvent and extracted hydrocarbons. The apparatusof this invention is further provided with means for solid/fluidseparation connected to the settling legs which means have a fluidoutlet and a solids outlet. Separator means are connected to the fluidoutlet of the solid/fluid separation means. The overhead outlet of theseseparator means permits the withdrawal of primarily solvent while thebottom outlet of the separator means permits the withdrawal of heaviermaterial. The apparatus is further provided with dryer means connectedto the solids outlet of the solid/fluid separating means and this dryerhas a gas outlet and a solids outlet. The gas outlet is directly orindirectly connected to the inlet of the separator means. Finally, arecycle means is provided for which connects the overhead outlet of saidseparator means with the inlet chamber to permit recycling of thesolvent.

In a second variation of the apparatus embodiment of this invention, theinlet chamber is connected to a group of at least two stirred reactorsarranged in series and the means for solid/fluid separation has itsinlet connected to the outlet of said stiired reactors.

It is presently preferred that a lock hopper is connected with saidinlet chamber. Furthemore, a pressure pump is provided for for injectingthe solvent under pressure into said inlet chamber. The mixture ofdiatomaceous earth and solvent can be brought to the supercriticaltemperature condition by passing this mixture through a heater. Theheater is preferably an indirect heat exchanger

Yet further preferred features, details and embodiments will becomeapparent from the following specific examples as well as the descriptionof the drawing which are intended to illustrate the invention but not tounduly limit its scope.

EXAMPLE 1

Oil Bearing diatomaceous earth was supercritically extracted withn-heptane. 500 grams of oil laden diatomite ore from California U.S.A.,were placed in an unstirred reactor and purged with N₂. Heptane waspumped at 7 grams/minute to the reactor and the reactor was heated to400° C.(752° F.), and 1500 psig. This took about 2 hours and thistemperature is above the critical temperature of n-heptane of 267°C.(513° F.). After reading 400° C. an additional 500 cc of n-heptane waspumped to the autoclave until one more hour had elapsed. The autoclavewas then vented to a flask and the reactor was flushed with nitrogen.

The total contents were distilled in a batch distillation column to acut point of 120° C. at 1.47 psia. The residue was further distilled to120° C. at 10 mm Hg. The yield of final product (heptane free) was 94.0grams. Of the total heptane and diatomaecous earth used of 2039 totalgrams the loss was only 24.4 grams of 1.2% based upon total weight. This94.0 grams in 500 grams of diatomaceous earth was equivalent to 48.4gallons of oil yield per ton of earth using density by Fischer assay of0.962 average g/cc gravity of the product oil. In comparison 2 samplesof 100 grams/each of the same oil laden diatomaceous earth was retortedby Fischer assay to yield an average of 32.2 gals/ton. Thus the yield bysupercritical extractino of this diatomaceous earth was about 50.5 %greater than yield by Fischer assay.

EXAMPLE 2 (Comparative Run)

"Asphalt Ridge" Tar Sand was supercritically extracted with n-heptane.750 grams of "Asphalt Ridge" Tar Sand were placed in an unstirredreactor and purged with nitrogen. N-heptane solvent was pumped at 7grams per minute to the reactor and the reactor was heated to 400° C.(752° F.) and 1500 psig. This took about 2 hours and this temperature isabove the critical temperature of n-heptane of 267° C.(513° F.). Afterreaching 400° C. additional 500 grams of n-heptane was added to theautoclave by pumping at 400° C. until about one more hour had elapsed.The autoclave was then vented to a flask and the reactor was flushedwith nitrogen.

The total autoclave contents were distilled in a batch distillationcolumn to a cut point of 120° C. at 14.7 psia. The residue was furtherdistilled to 120° C. at 10 mm Hg. The yield of final product (heptanefree) was 86.7 grams. Of the total heptane and tar sand used of 2187.2total grams, the loss was only 15.7 grams or 0.72% based on totalweight.

This 86.7 grams in 750 grams of tar sand was equal to 30.55 gals of oilyield per tar using a density by Fischer assay of 0.9088 avg g/cc of theproduct tar oil. In comparison this "Asphalt Ridge" tar sand wasretorted by Fischer assay to yield an average of 23.5 gal/ton. Thus theyield by supercritical extraction of tar sand was about 30.55-23.5/23.5×100 or 30.0% greater than the yield by Fischer assay.

With Example 1 compared to Example 2 the improvement achieved bysupercritical extraction as compared to Fischer retorting fordiatomaceous earth compared with tar sand was 150.5/130.0 or 1.158 or15.8% higher for diatomaceous earth compared with tar sand.

This result shows that diatomaceous earth appears to be uniquelysuitable for supercritical extraction. Very high yields of hydrocarbonrecovery therefore appear possible utilizing the process of thisinvention.

In FIG. 1 of the drawing a first embodiment of the extraction stage ofthe process and apparatus of this invention is shown. Diatomaceous earthis fed from a lock hopper 1 into a mixing chamber 2. In this mixingchamber 2 the diatomaceous earth is blended, e.g. by means of a stirrer3 with solvent introduced from fresh solvent line 4 and/or recyclesolvent line 5 by means of a compression pump 6. The diatomaceousearth/solvent blend is passed via line 7 to heater 8. In heater 8 a fuelintroduced via line 9 is combusted and the diatomaceous earth/solventblend is heated by indirect heat exchanger with the combustion gases inheat exchange conduit 10.

The diatomaceous earth/solvent blend now under supercritical conditionsis introduced via line 11 into a loop reactor 12 and is moved in a loopin this loop reactor by means of, e.g. an impeller 13. The loop reactor12 is provided with at least two settling legs 14, each being equippedwith a set of two valves 15. These settling legs are operated so thatsolid material can settle in one settling leg, the upper valve beingopen the lower valve being closed. Then the upper valve of the settlingleg is closed and the lower valve is opened to discharge theconcentrated slurry of solid residue and fluid comprising solvent andextracted hydrocarbon. The settling and flushing operation is alternatedbetween the settling legs and it is possible to achieve a fairlyconstant flow of slurry from conduit 16.

In accordance with this invention it is possible to operate theextractor loop 12 at a much lower solids concentration than the one inmixing chamber 2 or line 16. Thereby a gradual enrichment of the fluidin the loop reactor 12 is possible. The loop reactor may either beflushed periodically completely to remove the oil rich fluid or thereactor can be operated until an equilibrium is reached. The advantageof this variation of the inventive process is that the actual extractionin the loop reactor 12 occurs at a much lower solids concentrationthereby allowing a more efficient extraction. The "reconcentration"occurs in the settling legs.

A second embodiment of the extraction portion of the process andapparatus of this invention is shown in FIG. 2. The same units have beenlabelled with the same numerals. Lock hopper and pressure pump have beenomitted. Instead of the loop reactor 12, a series of stirred contactors120, 121 and 122 are employed. These contactors are arranged in seriesand each of the contactor is equipped with a stirring mechanism 123,124, 125, respectively.

FIG. 3 shows a first variation of the recovery system or separating unitof the process and apparatus of this invention. The slurry of extractedand hydrocarbon depleted diatomaceous earth and fluid of solvent andextracted hydrocarbons is passed from line 16 into a solids/liquidseparation unit 19. This unit can be a cyclone or a series of cyclones,a simple settling vessel or a filter unit. In the arrangement shown inFIG. 3 a cyclone or settling unit is contemplated. An overhead of streamof substantially solid free hydrocarbons is withdrawn from thisseparating unit 19 via line 20. This material in line 20 is passedthrough a heater 35 to a separator 21. From the separating unit 21 anoverhead stream being substantially extract free solvent is withdrawnvia line 22. A bottoms stream containing the extracted hydrocarbonvalues is withdrawn from the separator unit 21 via line 23. This bottomsstreams is further subjected to solvent recovery in unit 24 which may bea stripper unit. A solvent stream leaves this solvent recovery unit 24via line 25. Steam can be injected into the solvent recovery unit vialine 26. Substantially solvent free hydrocarbon material is removed fromunit 24 via line 27. This hydrocarbon material can be subjected tofurther processing such as cracking or other refining operations.Streams 22 and 25 are combined in solvent stream line 41.

From the fluid/solids separator unit 19 a solid material containing somefluid is withdrawn, e.g. via a series of rotary valves or locks 28. Thehigh pressure of this solid material is thereby gradually reduced. Theproduce is then introduced via line 29 into a dryer 30. This dryer 30can be heated. Evaporated solvent leaves the dryer 30 via line 31. Thevast majority of the solvent to be recovered from the solid material inline 29 is already present as a solvent vapor in line 29 in view of thesubstantial reduction in pressure occurring in the valves 28. The dryer30 therefore has primarily a gas/solid disengaging function. However, itis within the scope of this invention to heat the dryer such as torecover any remaining solvent from the solid particles.

The solvent vapors from line 31 are at a significantly lower pressurethan the solvent leaving the separator 21. The solvent vapors in line 31are cooled and condensed in unit 32. A liquid solvent stream is passedvia line 33 and pump 34 and combined with the stream in line 41. Ifneeded, the temperature of the solvent recycle stream in line 5 can bechanged by passing it through a heat exchanger 17.

A yet further variation of the recovery system or separation unit ofthis invention is shown in FIG. 4. Instead of a cyclone or settler unit19 this embodiment utilizes a filter system as the solid/fluidseparator. The filter system in FIG. 4 comprises at least two filterunits 42. These filter units are operated in tandem for allowingbackwashing and regeneration of the filter. The valve mechanism has beenomitted in FIG. 4 for clarity. A filtrate effluent substantially free ofsolids is withdrawn from the filters 42 via line 43. The solid materialor residue is withdrawn from the filters periodically via line 44. Theremaining unit are substantially the same as those shown in FIG. 3.

Reasonable variations and modification which will become apparent tothose skilled in the art can be made from this invention withoutdeparting from the spirit and scope thereof.

What is claimed is:
 1. Apparatus for supercritical extraction ofdiatomaceous earth comprising(a) source means for providing a source ofdiatomaceous earth containing recoverable hydrocarbons, (b) operativelyconnected to said source means an inlet chamber wherein saiddiatomaceous earth and a solvent can be contacted with each other, (c) aloop reactor connected to said inlet chamber, said loop reactor havingconnected thereto at least two settling legs provided with valves forperiodic removal of settling mixtures comprising diatomaceous earth andsolvent and extracted hydrocarbon values, (d) connected to said settlinglegs solid/fluid separation means, having a fluid outlet and a solidsoutlet, (e) separator means connected to said fluid outlet whichseparator means have an overhead outlet for solvent removal and a bottomoutlet for the removal of heavier materials, (f) dryer means connectedto said solids outlet of said solid/fluid separator means having a gasoutlet and a solids outlet, said gas outlet being directly or indirectlyconnected to the inlet of said separator means, (g) recycle meansconnected to said overhead outlet and to said inlet chamber forrecycling solvent from said separator means to said inlet chamber.